CN1119853A - Continuous process for purifying perfluorochemical compositions - Google Patents
Continuous process for purifying perfluorochemical compositions Download PDFInfo
- Publication number
- CN1119853A CN1119853A CN94191579A CN94191579A CN1119853A CN 1119853 A CN1119853 A CN 1119853A CN 94191579 A CN94191579 A CN 94191579A CN 94191579 A CN94191579 A CN 94191579A CN 1119853 A CN1119853 A CN 1119853A
- Authority
- CN
- China
- Prior art keywords
- composition
- perfluorochemical
- hydrogen fluoride
- perfluor
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
- C07B63/02—Purification; Separation; Stabilisation; Use of additives by treatment giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a process for the purification of a perfluorochemical composition comprises continuously mixing the perfluorochemical composition, comprising a liquid mixture of inert perfluorochemicals and isomeric fluorohydrochemicals, with a stabilization composition comprising water-miscible alkanol and an aqueous solution of base made by dissolving the base in an amount of water sufficient to dissolve or disperse the fluoride salt by-products of the subsequent reaction of the base with the fluorohydrochemicals to form fluoroolefins.
Description
The present invention relates to a kind of purifying perfluorinated compound method for compositions that is used for, that is, and a kind of method that is used for separating substantially and randomly reclaiming the inertia perfluorochemical from the mixture of the fluoro hydrogen compound of inertia perfluorochemical and isomery.
Well-known perfluorochemical such as perfluoro alkane class, perfluor ethers and perfluoroalkyl tertiary amines are chemically inert basically.This inertia makes it be applicable to many industrial application, for example conducts heat and tests fluid, hydraulic fluid and the lubricant of bathing.And many inertia perfluorochemicals (and emulsion and dispersion) can biologically with chemically dissolve, transport and carry a large amount of oxygen, and this ability makes the component of these perfluorochemicals as " blood substitute ", it can be used for treating heart attack, outbreak and other blood vessel blockage, and as coronary angioplasty, the adjuvant of cancer radiation and chemotherapy.(referring to, for example, R.J.Kaufman, " with perfluorochemical delivery of medical oxygen " Biotechnology of blood, edited by J.Goldstein, Chapter 7, pages 127-62, Butterworth-Heinemann, Stoneham, MA (1991).)
The inertia perfluorochemical can be by electrochemical fluorination effect (ECF) preparation, but wherein makes electric current pass through the fluorizated organic starting compound and the anhydrous hydrogen fluoride mixtures of liquids produces a kind of fluorinated product.Yet, except needed perfluor mixture, also contain partially fluorinated compound or hydrogen fluoride compounds in this ECF product, they reduce the inertia of this product, therefore usually by using alkaline purification and distillation with its removal.(referring to, for example, Kirk-Oth-mer Encyclopedia of Chemical Technology, Third Edition, Vol-ume 10, pages 874-81 (especially page 878), John Wiley ﹠amp; NewYork (1980); Moore et al., J.Fluorine Chem.32,41 (especially page 60) (1986); And Nishimura et al., J.Printed Circuitry 6 (4), and 203 (1991) .) the inertia perfluorochemical also can prepare by directly fluoridizing, but wherein fluorizated organic starting compound and fluorine gas reaction.(referring to, for example, U.S. Patent No. 5,093,432 (Bierschenk et al.)) yet, directly fluoridize and also can produce the fluorinated product that contains some partially fluorinated compound or fluoro hydrogen compound, it need be removed (handling) usually so that the inertia of this product reaches maximum with alkali or other fluorine gas.(referring to, for example, the open No.WO 90/06296 (Minnesota Mining andManufacturing Company) of international monopoly, especially page 8.)
In U.S. Patent No. 4,929, narrated among 317 (the Tokuyama Soda KabushikiKaisha) by directly fluoridizing, ECF or other fluorination process obtain the difficulty of high purity Perfluorinate product, and it has disclosed a kind of method that is used to prepare perfluoro organic compound.This method comprise the first step organic compound that has hydrocarbon key is slowly fluoridized generate a kind of compound wherein number of fluorine atoms the ratio of number of hydrogen atoms is at least 8, and second step (purifying) made this mixture contact with molecular fluorine under 110 to 180 ℃ temperature.
U.S. Patent No. 4,035,250 (Walters et al.) have disclosed a kind of electrochemical fluorination that is used to produce perfluor-normal heptane and have comprised and will be cooled to the temperature that is enough to make this effluent condensation from the first pond effluent, from this condensation product, separate and be rich in the fluorocarbon phase, carrying out subordinate phase fluoridizes, wherein further fluoridized being rich in the partially fluorinated normal heptane of fluorocarbon in mutually, and separated the perfluor normal heptane from the subordinate phase effluent by simple fractionation.
U.S. Patent No. 4,029,552 (Fozzard) have also disclosed a kind of method that is used for obtaining from a kind of electrochemical fluorination product by a kind of new toluene/perfluor normal heptane constant boiling mixture high purity perfluor normal heptane.
U.S. Patent No. 3,737,470 (Cottle) have disclosed a kind of be used for separating and reclaiming fully halogenated fluorocarbon of mixture (for example perfluoro-carbon and/or cfc) and partially halogenated fluorocarbon (for example chlorine fluorine compound).This method comprises makes this partially halogenated hydrofluoric ether dehydrohalogenation become corresponding alkene, makes this alkene halogenation become fully halogenated fluorocarbon, and the resulting mixture of fractionation is to separate and to reclaim fully halogenated fluorocarbon.Dehydrohalogenation step available bases metal hydroxides or its solution or dispersion carry out (referring to the 6th be listed as the 29th walk to the 7th be listed as the 30th the row).
U.S. Patent No. 4,618,731 (Beck) have disclosed a kind of by R under the temperature that is higher than 80 ℃ (being 100-115 ℃ preferably) in the container of a sealing
fCH
2CH
2I and R
fI impurity and a kind of excessive alkali metal hydroxide (be sodium hydroxide preferably, it can be the aqueous solution, is listed as the 45th row referring to the 2nd) and a kind of C
1-C
3Alcohol (being Virahol preferably) reaction is until can not survey the method that iodide are used for purifying 2-perfluoroalkyl alcohol in final product.
Japanese patent application No.2-412800 (Tokuyama Sotatsu K.K.) has disclosed a kind of method for preparing perfluoro organic compound by the halogenation of organifying compound, this fluorizated product be selected from alkali metal hydroxide, alkaline earth metal hydroxides, secondary amine contacts with at least a alkali in the tertiary amine, and resulting product is contacted with molecular fluorine.This alkali uses with water or alcoholic solution form usually, obtains result preferably according to stating when this alkali is the mixture of a kind of alkali metal hydroxide or alkaline earth metal hydroxides and secondary amine or tertiary amine.
U.S. Patent No. 4,766,261 (Bierl) have disclosed a kind of by carbon fluoride contact with the strong basicity of a kind of dry basically (contain and be not more than 30% by weight) and the basic metal or the alkaline earth metal compound (for example a kind of metal hydroxides or a kind of inorganic or organo-metallic oxyhydroxide) of strong affinity, thus and the method for the degradation production purified carbon fluorochemical of separation generation.This compound can solid form such as granular, and powder or sheet perhaps also can be dispersed or dissolved in a kind of non-aqueous solvent such as the ethanol and use.
Briefly, the invention provides a kind of continuous processing that is used for purifying perfluorinated compound composition, that is, be used for from separate and randomly reclaim the continuous processing of nearly all inertia perfluorochemical as the mixture of directly fluoridizing or ECF obtains the hydrogen fluoride compounds of inertia perfluorochemical and isomery by fluorination process.This method comprises makes a kind of perfluorochemical composition that comprises a kind of inertia perfluorochemical (for example perfluoro alkane, perfluor ethers or perfluoroalkyl tertiary amines) and isomery hydrogen fluoride compounds and a kind of comprising mix with the miscible alkanol of water and the stable composition of alkali (as the potassium hydroxide) aqueous solution continuously.This alkaline solution can be by being prepared this alkali dissolution in the water of the by product that is enough to dissolve and disperses the reaction of this follow-up alkali and the hydrogen fluoride compounds in the perfluorochemical composition, wherein hydrogen fluoride compounds reaction back dehydrohalogenation becomes fluorinated olefin.The consumption of alkanol is converted into the required stoichiometry of alkoxyl group fully greater than the fluorinated olefin that will obtain.The resulting stable liquid mixture that comprises untreated perfluorochemical composition can be separated and form the upper strata water, fluorinated reactive hydrogen compound product phase, and the perfluorochemical phase is rich in lower floor.
Be preferably, used in the method for the invention alkanol is the alkanol (the perhaps mixture of one or more these alkanols) that contains 1 to 4 carbon atom and contains and be selected from alkali metal hydroxide, oxide compound and alkoxide above stoichiometry (with respect to the amount of hydrogen in the hydrogen fluoride compounds or " hydride "); Ammonium hydroxide; Primary amine, secondary amine and tertiary amine; And composition thereof alkaline aqueous solution.This method is preferably and comprises that also a step wherein is rich in perfluorochemical with the basic inertia perfluorochemical that reclaims from stable mixture by for example therefrom discharging lower floor.
Continuous processing of the present invention is a kind of simple, effective purifying perfluorinated compound method for compositions and provide a kind of method of low price can substitute batch process commonly used.This method can be removed, for example, and up to the hydrogen fluoride compounds component in the perfluorochemical composition more than 99%, according to the initial used reaction conditions of hydrogen fluoride compounds content in the composition.
The perfluorochemical composition of available method purifying of the present invention comprises such inertia perfluorochemical such as perfluoro alkane, the perfluoro alkane that Pentafluorosulfanyl replaces, perfluor ether, perfluor amino ethers, perfluoroalkyl tertiary amine and composition thereof.The perfluorochemical composition is generally fluoridation, for example, and the electrochemical fluorination reaction or the direct product of fluoridation, and typically comprise the mixture of one or more inertia perfluorochemicals and one or more isomery hydrogen fluoride compounds.In the perfluorochemical composition, also can there be low amount of fluorinated alkene, unreacted organic raw material compound, low-molecular-weight split product and high-molecular weight coupling product.Perfluorochemical in the perfluorochemical composition and hydrogen fluoride compounds component can contain a spot of chlorine, that is, and and the chlorine atom that is connected with carbon.The representative example of the inertia perfluorochemical that is suitable for comprises perfluoropropane, perfluorinated butane, perflenapent, perflexane, PF 5070, PFO, Perfluorononane, perfluoro decane, 1,8-dichloro PFO, 1-Pentafluorosulfanyl perfluorinated butane, 1-Pentafluorosulfanyl perflenapent, 1-Pentafluorosulfanyl perflexane, two (chlorobutyl) ether, the perfluoro butyl tetrahydrofuran (THF), perfluor-N-methylmorpholine, perfluor-N-ethylmorpholine, perfluor-N-sec.-propyl morpholine, perfluoro triethylamine, perfluamine, perfluorotributylamine, perfluor triamylamine and composition thereof.This method is for purifying C
3-C
9Perfluoro alkane, the perfluoro alkane that Pentafluorosulfanyl replaces, perfluor ether, the perfluor amino ethers, perfluoroalkyl tertiary amine and composition thereof is useful especially, works as C
3-C
9When compound generates alkoxy vinyl ethers relatively the high-molecular weight compound more can be dissolved in the alkanol aqueous solution (thereby easier from perfluorochemical, separate).Best is that this method is used for purifying C
3-C
6Perfluoro alkane, perfluor ether, perfluor amino ethers, perfluoroalkyl tertiary amine and composition thereof.
Used alkanol is to have to a certain degree and compatibility water and generally hydrogen fluoride compounds (the hydrogen fluoride compounds component reaction in alkali and perfluorochemical composition generates) can be transformed into alkoxy vinyl ethers (or other is by alkoxy vinyl ethers more highly oxidized compound with alkanol reaction generation) in the inventive method.The representative example of these alkanols comprises methyl alcohol, ethanol, propyl alcohol, butanols and composition thereof.Firsts and seconds C
1-C
4Alkanol and composition thereof is preferred, and this is because they have bigger and reactivity fluorinated olefin (with respect to the level Four alkanol).Methyl alcohol most preferably, this is reactive high with fluorinated olefin because its price is low.Use a kind of superstoichiometric alkanol (with respect to the amount that fluorinated olefin is converted into fully the required alkanol of alkoxy vinyl ethers), for example, there is unreacted alkanol in every mole of about 1 to 1000 mole of alkanol of hydride after fluorinated olefin is converted into alkoxy vinyl ethers.This unreacted alkanol helps purge process by improving alkoxy vinyl ethers in the solubleness of treated perfluorochemical composition aqueous phase.Be preferably, the consumption of alkanol is every mole of about 25 to 100 moles of alkanols of hydride.
Used alkali is generally those alkali that the hydrogen fluoride compounds component dehydrohalogenation that can make in the perfluorochemical composition generates fluorinated olefin in the inventive method.The alkali that is suitable for comprises ammonium hydroxide; Primary amine, secondary amine and tertiary amine; Alkalimetal oxide, oxyhydroxide and alkoxide; And composition thereof.The representative example of these alkali comprises ammonium hydroxide, methylamine, ethamine, dimethylamine, diethylamine, Trimethylamine 99, triethylamine, sodium oxide, potassium oxide, Lithium Oxide 98min, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, methoxyl group potassium, methoxyl group lithium, Sodium Ethoxide, oxyethyl group potassium, oxyethyl group lithium and composition thereof.Alkali comprises alkali metal hydroxide preferably, ammonium hydroxide and composition thereof, and this is because it is cheap.Best is potassium hydroxide, because it is inexpensive, be easy to get, and the fluorochemical salt (as the by product of de-hydrogen halide) that produces can be suitably water-soluble.Alkali uses wherein with the solution form, and the amount of water is enough to dissolving and disperses by product fluoride salt (under service temperature).Using so, the water of amount has reduced or eliminated the line clogging problem thereby has helped carrying out continuously of this operation.Be preferably, use enough water to dissolve this salt fully.Can use, for example, about 1 to 60% (weight) KOH basic solution.Be preferably, use superstoichiometric alkali (with respect to the amount of hydride in the hydrogen fluoride compounds), for example every mole of alkali that hydride is about 2 to 20 moles enables hydrogen fluoride is changed into fluorinated olefin fully.
Method of the present invention can be passed through, for example, bubbling is directed into a kind of mixture that contains inertia perfluorochemical composition and isomery hydrogen fluoride compounds in the opening or closed container (being preferably the reactor of a temperature and pressure control) that whipping appts is housed continuously, imports a kind of stable composition that contains alkanol and alkaline aqueous solution simultaneously continuously and carry out in this container.This stable composition can single fluid imports or goes into isolating alkanol and alkaline solution conductance.Water and alkali also can import respectively, though this is not preferred.(the perfluorochemical composition comprises the head product itself (when it is recovered or removes) from fluorination reactor, perhaps can comprise process preliminary purification step as distillation, crystallization or liquid-liquid extraction are to reduce the head product of the content of hydrogen fluoride compounds in the composition before importing container.) the suitable residence time will be with the heterogeneous states of perfluorochemical to make perfluorochemical composition and stable composition bonded in this container, the content of hydride in the perfluorochemical composition, the temperature and pressure condition, stirring extent, the character of alkali, the purity of the concentration of alkali and needed product in the stable composition and changing.The suitable residence time can be determined by the content of hydride in the monitoring inertia perfluorochemical product.For hydride content is the perfluoro alkane of about 0.001 to 0.1% (weight), and 6 to 8 hours the residence time is useful.Stir the contact that helps reactant in the container preferably, the temperature and pressure of container can remain on inertia perfluorochemical and hydrogen fluoride compounds are kept under any temperature and pressure of liquid phase, it provides a kind of needed speed of response, that is, make hydrogen fluoride compounds change the needed speed of alkoxy vinyl ethers into.Can use the pressure of about 0 to 250 ℃ temperature and about 0.1MPa to 10MPa (1 to 100 normal atmosphere).Be preferably, use the pressure of about 0 to 150 ℃ temperature and about 0.1MPa to 2MPa (1 to 20 normal atmosphere).
The fluid (containing the inertia perfluorochemical, water, alkanol, alkoxy vinyl ethers and any unreacted alkali and unreacted hydrogen fluoride compounds) that contains product can be discharged (continuous or semi-continuous) from container.This fluid can pass through a phase separation container, for example, decantor, there be separated form lower floor be rich in perfluorochemical mutually and the upper strata contain the water of alkoxy vinyl ethers.Be preferably, be rich in perfluorochemical by discharge lower floor from container or decantor and reclaim (continuous or semi-continuous) nearly all inertia perfluorochemical mutually.If desired, this nearly all inertia perfluorochemical can be by such device as distillation, make perfluorochemical contact (for example by making the fluorine gas bubbling) with fluorine gas, perhaps make perfluorochemical carry out adsorption treatment to be further purified or " making with extra care " (with its hydrogen fluoride compounds content of further minimizing) with silica gel, molecular sieve or gac then through washing by the liquid perfluorochemical.
Continuous processing of the present invention is useful as being used for a kind of simple effective method that purifying contains the perfluorochemical composition of inertia perfluorochemical (for example perfluoro alkane, perfluor ether and perfluoroalkyl tertiary amine) and isomery hydrogen fluoride compounds.These can easily and effectively carry out purifying by the fluoridation method by this method as the perfluorochemical composition of directly fluoridizing or ECF produces, and expense is lower than common batch process.
The present invention is further described by the following examples, and still concrete material and amount of being mentioned in these embodiments, and other condition and details should not constitute unsuitable restriction of the present invention.Embodiment 1 contains the purifying of the perfluorochemical composition of perfluor-N-methylmorpholine
The thick perfluorochemical composition that contains perfluor-N-methylmorpholine by the electrochemical fluorination prepared in reaction of N-methylmorpholine.With a packed column reaction products resulting is carried out fractionation, and fraction is carried out
1H NMR analyzes the hydride of demonstration 0.0047% (weight) (corresponding to molecular formula C
5ONH
xF
11-x, wherein the form of x=1-11 hydrogen fluoride compounds isomer random mixture exists).The fractionation composition that obtains is injected a 600ml with the speed of 150g/hr (0.33lb/hr), three grades, temperature control and pressure control, (it is equipped with first lower floor inlet and is used to import stable composition stirred-tank reactor, second lower floor inlet is used to import the perfluorochemical composition, and upper strata outlet is used for discharging the fluid that contains product), the stable composition in water and carbinol mixture (the KOH aqueous solution of 45% (weight) being diluted to 10% (weight) with methyl alcohol) that will contain 10% KOH simultaneously injects this reactor with the speed of 10 to 12g/hr (0.022-0.026lbs/hr).These velocity of flow are equivalent to 2.5 moles of KOH of every mole of hydride (in thick perfluorochemical composition) and every mole of hydride 34.7 mole, of methanol.This reactor remains under barometric point and the 25 ℃ of temperature, uses the stirring velocity of 300rpm.The residence time of reactant is 7 hours in the reactor.
The stable fluid collection that contains product that obtains in the reactor in a flask, is transferred in the separating funnel, and makes it be separated into the upper strata water to be rich in perfluorochemical mutually with lower floor.The perfluorochemical that is rich in of lower floor is discharged from funnel, wash with water, then by a packed column that contains silica gel.Perfluor-N-methylmorpholine that recovery is obtained carries out
1H NMR analyzes and shows the hydride that contains 0.0023% (weight), shows that the content of hydride in the perfluorochemical composition has reduced about 50%.Embodiment 2
The thick perfluorochemical composition that contains perflenapent by the electrochemical fluorination prepared in reaction of pentane.The purifying thing (or thick composition) that the perfluorochemical composition that contains perflenapent is produced in resulting reaction with a packed column carries out fractionation, and fraction is carried out
1HNMR analyzes the hydride of demonstration 0.0015% (weight) (corresponding to molecular formula C
5H
xF
12-x, wherein the form of x=1-12 hydrogen fluoride compounds isomer random mixture exists).
The fractionation composition that obtains is injected a 7.6l (2 gallons) with the speed of 820g/hr (1.80lb/hr), six grades, temperature control and pressure control, (it is equipped with first lower floor inlet and is used to import stable composition stirred-tank reactor, second lower floor inlet is used to import the perfluorochemical composition, and upper strata outlet is used for discharging the fluid that contains product), the stable composition in water and carbinol mixture (the KOH aqueous solution of 45% (weight) being diluted to 20% (weight) with methyl alcohol) that will contain 20% KOH simultaneously injects this reactor with the speed of 290g/hr (0.64lb/hr).This reactor remains under the pressure and 100 ℃ of temperature of 549kPa (65psig), uses the stirring velocity of 1000rpm.The residence time of reactant is 9.7 hours in the reactor.
The stable fluid collection that contains product that obtains in the reactor is kept being separated into the upper strata water immediately at there and being rich in perfluorochemical mutually with lower floor in 15.5 ℃ the jacket layer container at one.The perfluorochemical that is rich in of part lower floor is discharged mutually from container, wash with water, then by a packed column that contains silica gel.The perflenapent that recovery is obtained carries out
1H NMR analyzes the hydride that only contains 0.00047% (weight) in the perfluorochemical composition that is presented at purifying.
With Arcus et al., Testing for Chemical Inertness in ElectronicCoolants, Int.Electronic Circuit Packaging Symposium, 10thSymposium, program described in the paper 2/4,1969 is also analyzed the remaining hydride of the perfluorochemical composition sample that reclaims.Use this program, this sample is contacted with piperidines, water extraction then.Then make the aqueous solution that obtains by anionite-exchange resin to remove piperidines, measure " free fluorochemical " (producing) with fluoride ion selective electrode by the fluorinated hydrocarbons dehydrofluorination.Analytical results and purification condition are comprehensively listed in table 1.Embodiment 3-5 contains the purifying of the perfluorochemical composition of perflenapent
With method substantially the same manner as Example 2 other sample of fractionated composition among the embodiment 2 is carried out purifying, use the stable composition of identical device and use same concentrations, but use various temperature, pressure, stirring velocity, feed rate and the residence time.Reclaim the sample of resulting purifying and analyze with method substantially the same manner as Example 2.Below purification condition and analytical results (as can be seen in the sample of purifying only the hydride of remaining minute quantity) are listed in the table 1.
Table 1
Embodiment 6
| The embodiment numbering | Stirring velocity (rpm) | Temperature (℃) | Pressure (kPa) | The feed rate of perfluorochemical composition (g/hr) | The feed rate of stable composition (g/hr) | The residence time (Hrs) | Final free fluorochemical (μ g/g) | Record hydride final weight % (X10 by 1H NMR -4) |
| ????2 | ????1000 | 100 | ?549 | ??820 | ????290 | ????9.7 | ????0.2 | ????4.7 |
| ????3 | ????1000 | 100 | ?549 | ??1,940 | ????77 | ????6.1 | ????0.5 | ????5.2 |
| ????4 | ????500 | 100 | ?549 | ??1,990 | ????82 | ????6.0 | ????＜1 | ????7.4 |
| ????5 | ????1000 | 129 | ?618 | ??1,820 | ????145 | ????6.2 | ????1.8 | ????6.3 |
The thick perfluorochemical composition that contains perflexane by the electrochemical fluorination prepared in reaction of hexane.With a packed column reaction products resulting (or thick composition) is carried out fractionation, and fraction is carried out
1H NMR and gas chromatographic analysis show that the hydride of 0.0024% (weight) is (corresponding to molecular formula C
6H
xF
14-x, wherein the form of x=1-14 hydrogen fluoride compounds isomer random mixture exists).
The fractionation composition that obtains is injected the 7.6l (2 gallons) described in the embodiment 2 with the speed of 660g/hr (1.45lb/hr), six grades, temperature control and pressure control, (it is equipped with first lower floor inlet and is used to import stable composition stirred-tank reactor, second lower floor inlet is used to import the perfluorochemical composition, and upper strata outlet is used for discharging the fluid that contains product), the stable composition in water and carbinol mixture (the KOH aqueous solution of 45% (weight) being diluted to 20% (weight) with methyl alcohol) that will contain 20% KOH simultaneously injects this reactor with the speed of 36g/hr (0.08lb/hr).This reactor remains under the pressure and 100 ℃ of temperature of 418kPa (46psig), uses the stirring velocity of 1000rpm.The residence time of reactant is 17.7 hours in the reactor.
The stable fluid collection that contains product that obtains in the reactor is kept being separated into the upper strata water immediately at there and being rich in perfluorochemical mutually with lower floor in 15.5 ℃ the jacket layer container at one.The perfluorochemical that is rich in of part lower floor is discharged mutually from container, wash with water, then by a packed column that contains silica gel.With method substantially the same manner as Example 2 the perflexane that recovery obtains is analyzed.The result is as shown in table 2, only contains the hydride of 0.000019% (weight) as can be seen in the perfluorochemical composition of purifying.Embodiment 7-9 contains the purifying of the perfluorochemical composition of perflexane
With method substantially the same manner as Example 6 other sample of fractionated composition among the embodiment 6 is carried out purifying, use identical device and stirring velocity, but use various temperature, pressure, the feed rate stable composition concentration and the residence time.Reclaim the sample of resulting purifying and analyze with method substantially the same manner as Example 6.Below purification condition and analytical results (as can be seen in the sample of purifying only the hydride of remaining minute quantity) are listed in the table 2.
Table 2
* by preparing with methyl alcohol dilution 45% (weight) KOH aqueous solution
| The embodiment numbering | Stirring velocity (rpm) | Temperature (℃) | Pressure (kPa) | The feed rate of perfluorochemical composition (g/hr) | The feed rate of stable composition (g/hr) | Stable composition *Concentration (weight %KOH is in water/methyl alcohol) | The residence time (Hrs) | Final free fluorochemical (μ g/g) | By 1HNMR records hydride final weight % (X10 -5) |
| ????6 | ????1000 | 100 | ??418 | ????660 | ????36 | ????20 | ????17.7 | ????1.5 | ????1.9 |
| ????7 | ????1000 | 100 | ??480 | ????590 | ????41 | ????20 | ????19.3 | ????1.5 | ????1.9 |
| ????8 | ????1000 | 100 | ??446 | ????510 | ????268 | ????12.9 | ????13.2 | ????0.02 | ????1.2 |
| ????9 | ????1000 | 100 | ??446 | ????1,160 | ????268 | ????12.9 | ????7.9 | ????0.01 | ????2.4 |
The present invention is carried out various conversion and replaces it will be readily apparent to those skilled in the art that, thereby do not exceed scope and spirit of the present invention.
Claims (10)
1. a method that is used for purifying perfluorinated compound composition comprises and can mix with the stable composition of the aqueous solution of the miscible alkanol of water and a kind of alkali the perfluorochemical composition that makes continuously described a kind of liquid mixture that comprises a kind of inertia perfluorochemical and isomery hydrogen fluoride compounds and a kind of comprising; This aqueous slkali is by being prepared in the water that described alkali is dissolved in the fluoride salt accessory substance that is enough to dissolve and disperses described alkali and the reaction of described hydrogen fluoride compounds, and the amount of alkanol is greater than fluorinated olefins being converted into fully the required stoichiometry of alkoxy vinyl ethers in the described stable composition.
2. the method for claim 1 also comprises the basic step that reclaims the inertia perfluorochemical from the stable composition that obtains.
3. the method for claim 1 is characterized in that described perfluorochemical composition comprises the head product from fluorination reactor.
4. method as claimed in claim 3 is characterized in that described perfluorochemical composition process prepurification step is to reduce hydrogen fluoride compounds content in the described composition.
5. method as claimed in claim 4 is characterized in that described prepurification step is distillation.
6. the method for claim 1 is characterized in that described alkali is selected from C
1-C
4Alkanol and composition thereof; Described alkali is selected from ammonium hydroxide; Primary amine, secondary amine and tertiary amine; Alkalimetal oxide, oxyhydroxide and alkoxide; And composition thereof; And described inertia perfluorochemical is selected from perfluoro alkane, the perfluoro alkane that perfluor sulfane base replaces, perfluor ether, perfluor amino ethers, perfluoroalkyl tertiary amine and composition thereof.
7. method as claimed in claim 6 is characterized in that described alkanol is selected from firsts and seconds C
1-C
4Alkanol and composition thereof; Described alkali is selected from alkali metal hydroxide, ammonium hydroxide and composition thereof; And described inertia perfluorochemical is selected from C
3-C
9Perfluoro alkane, C
3-C
9The perfluoro alkane that perfluor sulfane base replaces, C
3-C
9Perfluor ether, C
3-C
9The perfluor amino ethers, C
3-C
9The perfluoroalkyl tertiary amine, and composition thereof.
8. the method for claim 1 is characterized in that described alkaline solution contains the stoichiometry of the amount of described alkali above hydride amount in the hydrogen fluoride compounds.
9. the method for claim 1 is characterized in that the amount that alkaline solution contains water is enough to dissolve described fluorochemical by product.
10. one kind is used for purifying perfluorinated compound method for compositions it comprises that (a) distills head product from fluorination reactor, and described product comprises that (i) is selected from C
3-C
6Perfluoro alkane, C
3-C
6Perfluor ether, C
3-C
6The perfluor amino ethers, C
3-C
6The perfluoroalkyl tertiary amine, and composition thereof and the (ii) mixture of isomery hydrogen fluoride compounds; (b) resulting product of distillation is mixed with a kind of stable composition of methyl alcohol and potassium hydroxide aqueous solution that comprises, described potassium hydroxide aqueous solution is enough to dissolve described potassium hydroxide and the reaction of described hydrogen fluoride compounds and generates in the water of fluoride salt by product of fluorinated olefin and be prepared by described potassium hydroxide is dissolved in, the amount of potassium hydroxide described in the described aqueous solution is greater than the stoichiometry of hydrogen fluoride amount in the hydrogen fluoride compounds, and the amount of methyl alcohol described in the described stable compound is greater than the stoichiometry that described fluorinated olefin is converted into fully the alkoxy vinyl ethers aequum; (c) from the stable product that obtains, reclaim nearly all inertia perfluorochemical; (d) the inertia perfluorochemical of the basic recovery that obtains is washed and silica gel treatment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/039,861 | 1993-03-30 | ||
| US08/039,861 US5352785A (en) | 1993-03-30 | 1993-03-30 | Continuous process for purifying perfluorochemical compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1119853A true CN1119853A (en) | 1996-04-03 |
| CN1044228C CN1044228C (en) | 1999-07-21 |
Family
ID=21907717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94191579A Expired - Fee Related CN1044228C (en) | 1993-03-30 | 1994-02-14 | Continuous process for purifying perfluorochemical compositions |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5352785A (en) |
| EP (1) | EP0688309B1 (en) |
| JP (1) | JPH08508482A (en) |
| CN (1) | CN1044228C (en) |
| DE (1) | DE69406275T2 (en) |
| WO (1) | WO1994022794A1 (en) |
| ZA (1) | ZA941502B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145561A (en) * | 2013-03-01 | 2013-06-12 | 上海华捷视医疗设备有限公司 | Continuous production method for perfluoro tripropylamine |
| CN107176737A (en) * | 2016-03-10 | 2017-09-19 | 中昊晨光化工研究院有限公司 | The method that fluorine carbon solvent is extracted from perfluoro caprylic acid electrolysis by-products |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4205341A1 (en) * | 1992-02-21 | 1993-08-26 | Pharmpur Gmbh | METHOD FOR CLEANING PERFLUOR CARBON AND USE OF CLEANED PERFLUOR CARBON |
| DE4241969A1 (en) * | 1992-12-12 | 1994-06-16 | Hoechst Ag | High purity perfluoro (4-methyl-2-pentene), its preparation and use |
| US7312052B1 (en) | 1993-12-08 | 2007-12-25 | Stratagene California | Polymerase compositions and uses thereof |
| US5663127A (en) * | 1994-07-29 | 1997-09-02 | Minnesota Mining And Manufacturing Company | Perfluoropolyether lubricating compositions |
| US5750797A (en) * | 1996-04-15 | 1998-05-12 | Minnesota Mining And Manufacturing Company | Process for the production of hydrofluoroethers |
| CA2283635A1 (en) | 1997-03-21 | 1998-10-01 | Stratagene | Polymerase enhancing factor (pef) extracts, pef protein complexes, isolated pef protein, and methods for purifying and identifying |
| IT1299036B1 (en) * | 1998-04-07 | 2000-02-07 | Ausimont Spa | PURIFICATION OF PERFLUOROPROPYLVINYLETER |
| US6375912B1 (en) * | 1999-08-16 | 2002-04-23 | Agere Systems Guardian Corp. | Electrochemical abatement of perfluorinated compounds |
| GB0031303D0 (en) * | 2000-12-21 | 2001-01-31 | Ici Plc | Process for the purification of fluoromethyl hexafluoroisopropyl ether |
| US7053253B1 (en) * | 2005-05-02 | 2006-05-30 | 3M Innovative Properties Company | Process for purifying hexafluoropropene dimers |
| JP6648656B2 (en) * | 2016-08-31 | 2020-02-14 | 三菱マテリアル株式会社 | Sample analysis method |
| KR102704746B1 (en) * | 2022-06-21 | 2024-09-06 | 에스케이스페셜티 주식회사 | Equipment and method for fabricating high purity PFTPA |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3737470A (en) * | 1970-06-08 | 1973-06-05 | Phillips Petroleum Co | Separation and recovery of perhalogenated fluorocarbons |
| US4029552A (en) * | 1975-10-24 | 1977-06-14 | Phillips Petroleum Company | Process for obtaining high purity perfluoro-n-heptane |
| US4035250A (en) * | 1976-03-11 | 1977-07-12 | Phillips Petroleum Company | Production of perfluoro-n-heptane |
| CA1262346A (en) * | 1983-10-31 | 1989-10-17 | Thomas W. Bierl | Purification of fluorocarbons |
| US4766261A (en) * | 1984-09-17 | 1988-08-23 | Adamantech, Inc. | Purification of fluorocarbons |
| US4618731A (en) * | 1985-11-20 | 1986-10-21 | E. I. Du Pont De Nemours And Company | Process for purifying 2-perfluoroalkylethanols |
| EP0271272B1 (en) * | 1986-12-01 | 1992-04-15 | Tokuyama Corporation | Process for preparation of perfluoro organic compounds |
| US5093432A (en) * | 1988-09-28 | 1992-03-03 | Exfluor Research Corporation | Liquid phase fluorination |
| WO1990006296A1 (en) * | 1988-12-02 | 1990-06-14 | Minnesota Mining And Manufacturing Company | Direct fluorination process for making perfluorinated organic substances |
| DE4019061A1 (en) * | 1989-08-30 | 1991-03-07 | Kali Chemie Ag | New and known perfluorinated N-cycloalkyl cyclic amine derivs. |
| US4973774A (en) * | 1989-11-02 | 1990-11-27 | E. I. Du Pont De Nemours And Company | Chlorofluorohydrocarbon purification process |
| JP2834586B2 (en) * | 1990-12-21 | 1998-12-09 | 株式会社トクヤマ | Method for producing perfluoro organic compound |
| DE4115025A1 (en) * | 1991-05-08 | 1992-11-12 | Hoechst Ag | METHOD FOR REMOVING OLEFINIC IMPURITIES FROM 1,1,1,2,3,3,3-HEPTAFLUORPROPANE |
-
1993
- 1993-03-30 US US08/039,861 patent/US5352785A/en not_active Expired - Lifetime
-
1994
- 1994-02-14 WO PCT/US1994/002099 patent/WO1994022794A1/en active IP Right Grant
- 1994-02-14 CN CN94191579A patent/CN1044228C/en not_active Expired - Fee Related
- 1994-02-14 JP JP6522063A patent/JPH08508482A/en active Pending
- 1994-02-14 DE DE69406275T patent/DE69406275T2/en not_active Expired - Fee Related
- 1994-02-14 EP EP94909818A patent/EP0688309B1/en not_active Expired - Lifetime
- 1994-03-03 ZA ZA941502A patent/ZA941502B/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145561A (en) * | 2013-03-01 | 2013-06-12 | 上海华捷视医疗设备有限公司 | Continuous production method for perfluoro tripropylamine |
| CN103145561B (en) * | 2013-03-01 | 2014-07-16 | 上海华捷视医疗设备有限公司 | Continuous production method for perfluoro tripropylamine |
| CN107176737A (en) * | 2016-03-10 | 2017-09-19 | 中昊晨光化工研究院有限公司 | The method that fluorine carbon solvent is extracted from perfluoro caprylic acid electrolysis by-products |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1044228C (en) | 1999-07-21 |
| EP0688309B1 (en) | 1997-10-15 |
| EP0688309A1 (en) | 1995-12-27 |
| DE69406275D1 (en) | 1997-11-20 |
| DE69406275T2 (en) | 1998-05-20 |
| JPH08508482A (en) | 1996-09-10 |
| WO1994022794A1 (en) | 1994-10-13 |
| US5352785A (en) | 1994-10-04 |
| ZA941502B (en) | 1995-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1044228C (en) | Continuous process for purifying perfluorochemical compositions | |
| CN102936536B (en) | Intergrated chemical processe for industrial utilization of seed oils | |
| EP1177184B1 (en) | Polyfluorinated epoxides and associated polymers and processes | |
| EP1244644B1 (en) | Process for the elimination of materials containing hydrolyzable halides and other high molecular weight materials from epihalohydrin derived epoxy resins | |
| CN1075313A (en) | The preparation of fluorinated functional compounds | |
| US8759567B2 (en) | Process for producing perfluoro organic peroxide | |
| JP2002087997A (en) | Process for dehydrohalogenation of halogenated compound | |
| EP0482938A1 (en) | Synthesis of fluorinated ethers | |
| US4965379A (en) | Fluoroepoxides and a process for production thereof | |
| JP2004345967A (en) | Method for producing fluorine-containing ether compound | |
| CN101528719A (en) | Process for production of hexafluoropropylene oxide | |
| EP0980348B1 (en) | Process for purifying fluoromethyl 1,1,1,3,3,3-hexafluoroisopropyl ether | |
| CN116969825B (en) | Purifying method of perfluoro-hexanone | |
| CN1027061C (en) | Extractive distillation | |
| DE60300207T2 (en) | Sulfur pentafluoride compounds, process for their preparation and their use | |
| US6252105B1 (en) | Synthesis of low-fluoride organic compounds | |
| CN1276903C (en) | Method for producing hexafluoroethane and its use | |
| EP0414569A2 (en) | Three-liquid-phase epoxidation of perfluoroolefins | |
| CN1207256C (en) | Production of organic compounds which are low in fluoride | |
| JP4732704B2 (en) | Ionic liquid and method for producing the same | |
| CN1073424A (en) | Synthesizing of N-perfluorooctyl bromide | |
| US3598874A (en) | Preparation of chlorohydrins by reacting hypochlorous acid and long-chain olefins | |
| JP2000256229A (en) | Production of perfluoroalkanes | |
| CN1274662C (en) | Method for preparing ester glyoxalic acid | |
| CN112675795A (en) | System and method for preparing fatty alcohol polyether carboxylic acid by using microreactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |